WO2013094693A1 - Composition de caoutchouc pour pneus et pneu l'utilisant - Google Patents

Composition de caoutchouc pour pneus et pneu l'utilisant Download PDF

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WO2013094693A1
WO2013094693A1 PCT/JP2012/083103 JP2012083103W WO2013094693A1 WO 2013094693 A1 WO2013094693 A1 WO 2013094693A1 JP 2012083103 W JP2012083103 W JP 2012083103W WO 2013094693 A1 WO2013094693 A1 WO 2013094693A1
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group
carbon atoms
conjugated diene
residue
atom
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PCT/JP2012/083103
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Japanese (ja)
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成晃 松尾
礼子 矢木
亮多 玉手
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株式会社ブリヂストン
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a tire rubber composition and a tire using the same, and more specifically, the tire rubber is improved in dispersibility of a white filler such as silica in the tire rubber composition and excellent in low loss performance.
  • the present invention relates to a composition and a tire using the composition.
  • silica has been used as a filler to achieve both low loss performance (low fuel consumption) and grip on wet roads for the purpose of saving fuel consumption in automobiles. Formulation is frequently used.
  • the silica used tends to aggregate particles due to hydrogen bonding of silanol groups, which are surface functional groups, and it is necessary to lengthen the kneading time in order to improve the dispersion of the silica in the rubber. Further, since the dispersion of silica in the rubber is insufficient, the Mooney viscosity of the rubber composition is increased, and the processability such as extrusion is inferior.
  • the surface of the silica particles is acidic, the basic substance used as a vulcanization accelerator is adsorbed, the rubber composition is not sufficiently vulcanized, and the storage elastic modulus does not increase. Was. For this reason, there has been a demand for improvement in processability and the like in a silica-containing rubber composition.
  • a technique for improving processability and the like in a silica-containing rubber composition for example, 1) As processing aid for improving dispersion of reinforcing silica filler in rubber composition, polar terminal showing weak chemical reactivity with silica and non-polar showing weak chemical reactivity with elastic polymer A technique of adding an amide compound having a terminal (fatty acid amide) to a silica-containing rubber (for example, see Patent Document 1); 2) A technique for improving fuel economy and wear resistance by using silica surface-treated with a dialkanolamide and a silane coupling agent (see, for example, Patent Document 2) is known.
  • Patent Document 1 describes that processability is improved by adding an amide compound (fatty acid amide) having a structure different from that of the present invention to silica-containing rubber, but the silica dispersion effect is still sufficient.
  • the said patent document 2 uses the silica surface-treated with dialkanol amide and a silane coupling agent, the subject that this is also not enough as an improvement of the dispersibility of silica, and a low-loss performance. There is something.
  • a silica-containing diene rubber composition a rubber composition characterized in that 1 to 10 parts by weight of a specific tall oil fatty acid imidazoline is added to 100 parts by weight of the diene rubber component, and the rubber A pneumatic tire using the composition for a tire tread (for example, see Patent Document 3) is known.
  • the rubber composition of Patent Document 3 improves the processability by adding a specific tall oil fatty acid imidazoline to the silica-containing diene rubber composition, and at the same time has low heat buildup and wear resistance after vulcanization.
  • this rubber composition still has a problem that the dispersibility of silica and the low loss performance are not sufficient.
  • JP 2003-533574 A (claims, examples, etc.) JP 2010-59272 A (Claims, Examples, etc.) JP 2008-13619 A (Claims, Examples, etc.)
  • the present invention intends to solve the above-mentioned problems of the prior art, and improves the dispersibility of white fillers such as silica in the rubber composition to further improve the dispersibility of white fillers.
  • an object of the present invention is to provide a tire rubber composition and a tire using the same, in which the low loss performance is remarkably improved.
  • a white filler and a specific compound are used for at least one rubber component selected from natural rubber and / or diene-based synthetic rubber.
  • the rubber composition for tires described above and a tire using the tire composition can be obtained by containing a specific conjugated diene polymer as the rubber component, and the present invention is completed. It came to do.
  • the present invention resides in the following (1) to (11).
  • (1) For at least one rubber component (A) selected from natural rubber and / or diene-based synthetic rubber, at least one of compounds represented by the following general formulas (I) and (II): And the rubber component (A) contains at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom, in a polymerization active terminal, a polymerization start terminal and a polymerization chain.
  • a rubber composition for tires comprising a conjugated diene polymer contained in any of the above.
  • R 1 represents an alkyl or alkenyl group having 1 to 24 carbon atoms, a group represented by the following formula (III), wherein the alkyl group and alkenyl group are linear or branched. Either a chain or a ring may be used, and R 2 and R 3 may be a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit, and these may be the same or different.
  • R 4 represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic, and , R 5 is a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit.
  • A is a single bond or an alkyl or alkenyl group having 1 to 24 carbon atoms
  • B is a carbonyl group, an ester group, an amino group, an amide group, an ether group, a hydroxyl group
  • R 6 represents a C 1-24 alkyl group or alkenyl group
  • the alkyl group and alkenyl group may be linear, branched, or cyclic.
  • the tire rubber composition according to (1), wherein the conjugated diene polymer is a copolymer of an aromatic vinyl compound and a conjugated diene compound.
  • the conjugated diene polymer contains an aromatic vinyl compound unit of 0% by mass to 60% by mass and the vinyl bond content in the conjugated diene moiety is 5% by mass to 80% by mass.
  • the rubber composition for tires according to (3) is obtained by subjecting a polymerization active end to a compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom after the polymerization reaction.
  • the modified conjugated diene polymer has the following general formula (IV) at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
  • RaMXb ......... (IV) [In the formula (IV), each R independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • M is tin or silicon and X is independently chlorine, bromine or iodine.
  • A is an integer of 0 to 3
  • each of R 1 and R 2 independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms.
  • M is tin or silicon.
  • A is an integer of 0 to 3
  • the tire rubber composition according to the above (5) which is a modified conjugated diene polymer obtained by reacting with a rubber.
  • the modified conjugated diene polymer has the following general formula (VI): at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
  • a + b + c 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and D is a saturated cyclic tertiary amine compound] Residue, unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, A carboxylic acid halogen compound residue and at least one functional group selected from a hydrolyzable group-containing secondary amino group or mercapto group
  • R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R 1 is plural. May be different.
  • R 2 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 2 is plural, they are the same or different.
  • R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 3 is plural, they may be the same or different. Good.
  • A is an integer of 0 to 3
  • b is an integer of 1 to 4
  • a + b 4]
  • D is a saturated cyclic tertiary amine compound
  • Residue unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, A carboxylic acid halogen compound
  • R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R 1 is plural. May be different.
  • R 2 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 2 is plural, they are the same or different.
  • R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 3 is plural, they may be the same or different. .
  • the rubber component contains 5 to 200 parts by weight of a white filler and 0.5 to 15 parts by weight of the compound represented by the formula (I) with respect to 100 parts by weight of the rubber component.
  • a tire rubber composition in which low loss performance is remarkably improved by further improving dispersibility of a white filler such as silica in the tire rubber composition, and a tire using the same. Is done.
  • the rubber composition for tires of the present invention comprises a white filler and the following general formulas (I) and (II) with respect to at least one rubber component (A) selected from natural rubber and / or diene-based synthetic rubber. And at least one selected from the group consisting of a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom in the rubber component (A). It contains a conjugated diene polymer contained in either the initiation terminal or the polymer chain.
  • R 1 represents an alkyl or alkenyl group having 1 to 24 carbon atoms, a group represented by the following formula (III), wherein the alkyl group and alkenyl group are linear or branched. Either a chain or a ring may be used, and R 2 and R 3 may be a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit, and these may be the same or different.
  • R 4 represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic, and , R 5 is a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit.
  • A is a single bond or an alkyl or alkenyl group having 1 to 24 carbon atoms
  • B is a carbonyl group, an ester group, an amino group, an amide group, an ether group, a hydroxyl group
  • R 6 represents a C 1-24 alkyl group or alkenyl group
  • the alkyl group and alkenyl group may be linear, branched, or cyclic.
  • ⁇ Rubber component (A)> In the tire rubber composition of the present invention, as the rubber component (A), at least one rubber component selected from natural rubber and / or diene-based synthetic rubber is used. Rubber components that can be used include natural rubber (NR), diene synthetic rubber, unmodified styrene-butadiene copolymer (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), butyl rubber. (IIR), an ethylene-propylene copolymer, and the like can be used. These rubber components may be used singly or as a blend of two or more.
  • NR natural rubber
  • SBR unmodified styrene-butadiene copolymer
  • BR polybutadiene rubber
  • IR polyisoprene rubber
  • IIR an ethylene-propylene copolymer, and the like can be used. These rubber components may be used singly or as a blend of two or more.
  • the rubber component (A) of the present invention contains at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom in any of the polymerization active terminal, the polymerization starting terminal and the polymerization chain. It is necessary to contain a conjugated diene polymer. This is because the dispersibility of the white filler such as silica is further improved by incorporating the conjugated diene polymer having the above characteristics into the rubber component (A). That is, when a white filler such as silica is contained in the rubber component (A) containing the conjugated diene polymer having the above characteristics, the surface area of the white filler increases, and the surface area of the white filler increases.
  • the reaction point of the silica dispersant (hydrophobizing agent) composed of the compound represented by the general formula (I), formula (II) or the like increases.
  • a silica dispersant (hydrophobizing agent) comprising a compound represented by general formula (I), formula (II) or the like silica or the like
  • the dispersibility of the white filler is further improved.
  • the conjugated diene polymer used in the present invention can be produced as a polymer having an organometallic active site in the molecule, and the production method is not particularly limited, and is a solution polymerization method, a gas phase polymerization method, Any of the bulk polymerization methods can be used, but the solution polymerization method is particularly preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition
  • the active site metal is preferably one selected from alkali metals and alkaline earth metals, and lithium metal is particularly preferable.
  • a target polymer can be produced by anionic polymerization of a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound using a lithium compound as a polymerization initiator.
  • a conjugated diene polymer in the present embodiment a conjugated diene polymer obtained by copolymerizing a (co) polymer of a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound from the viewpoint that the glass transition temperature can be controlled. Polymers are preferred.
  • the (co) polymer means a polymer or a copolymer.
  • a halogen-containing monomer and activate the halogen atom in the polymer with an organometallic compound.
  • organometallic compound for example, it is also effective to lithiate the bromine moiety of a copolymer containing an isobutylene unit, a paramethylstyrene unit and a parabromomethylstyrene unit to form an active site.
  • the active site may be present in the polymer molecule, and may be present in any of the polymerization active terminal, the polymerization initiation terminal, and the polymerization chain.
  • the active site is located at the end of the polymer.
  • the compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom is reacted with the active terminal, the conjugated diene polymer in the present invention can be obtained. .
  • conjugated diene compound examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. These may be used alone or in combination of two or more, and among these, 1,3-butadiene and isoprene are particularly preferred.
  • aromatic vinyl compound used for copolymerization with these conjugated diene compounds include styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexyl.
  • the monomer concentration in the solvent is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 30% by mass.
  • the content of the aromatic vinyl compound in the charged monomer mixture is preferably in the range of 1 to 60% by mass, more preferably 5 to 45%. A range of mass% is preferred.
  • the lithium compound of the polymerization initiator is not particularly limited, but hydrocarbyl lithium and lithium amide compounds are preferably used.
  • hydrocarbyl lithium When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal.
  • a conjugated diene polymer having a polymerization active site is obtained.
  • the latter lithium amide compound When the latter lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained.
  • hydrocarbyl lithium those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable.
  • ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n- Examples include decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, reaction products of diisopropenylbenzene and butyl lithium. Of these, n-butyllithium is preferred.
  • lithium amide compound for example, lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethylamide, lithium diethylamide, lithium dibutylamide, lithium dipropylamide, Lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium methylbutyramide, lithium ethylbenzylamide And lithium methylphenethylamide.
  • cyclic such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, etc.
  • Lithium amide is preferred, and lithium hexamethylene imide and lithium pyrrolidide are particularly preferred.
  • These lithium amide compounds are generally prepared in advance from a secondary amine and a lithium compound in the polymerization, but can also be prepared in-polymerization in situ.
  • the amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.
  • a conventionally well-known method can be used. Specifically, in an organic solvent inert to the reaction, for example, in a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound are used.
  • the desired conjugated diene polymer can be obtained by subjecting the lithium compound as a polymerization initiator to anionic polymerization in the presence of a randomizer to be used, if desired.
  • the hydrocarbon solvent preferably has 3 to 8 carbon atoms.
  • the randomizer used as desired is control of the microstructure of the conjugated diene polymer, such as an increase in 1,2 bonds in the butadiene moiety in the butadiene-styrene copolymer, an increase in 3,4 bonds in the isoprene polymer, etc.
  • it is a compound having an action of controlling the composition distribution of monomer units in a conjugated diene compound-aromatic vinyl compound copolymer, for example, randomizing butadiene units or styrene units in a butadiene-styrene copolymer.
  • the randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used.
  • potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can also be used.
  • One of these randomizers may be used alone, or two or more thereof may be used in combination. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of lithium compound.
  • the temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C., more preferably in the range of 20 to 130 ° C.
  • the polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.
  • the glass transition point (Tg) obtained by differential thermal analysis of the obtained polymer or copolymer is preferably in the range of ⁇ 110 ° C. to ⁇ 15 ° C. It is difficult to obtain a polymer having a glass transition point of less than ⁇ 110 ° C., and when it exceeds ⁇ 15 ° C., the viscosity becomes too high in the room temperature region, which may make handling difficult.
  • the modified conjugated diene polymer is produced by coordination polymerization using a rare earth metal compound as a polymerization initiator
  • the following (A) component, (B) component, and (C) component may be used in combination: preferable.
  • the component (a) used for the coordination polymerization is selected from a rare earth metal compound, a complex compound of a rare earth metal compound and a Lewis base, and the like.
  • rare earth metal compounds include rare earth element carboxylates, alkoxides, ⁇ -diketone complexes, phosphates and phosphites, and Lewis bases include acetylacetone, tetrahydrofuran, pyridine, N, N -Dimethylformamide, thiophene, diphenyl ether, triethylamine, organophosphorus compounds, monovalent or divalent alcohols, etc.
  • the rare earth element of the rare earth metal compound lanthanum, neodymium, praseodymium, samarium and gadolinium are preferable, and among these, neodymium is particularly preferable.
  • component (a) examples include neodymium tri-2-ethylhexanoate, complex compounds thereof with acetylacetone, neodymium trineodecanoate, complex compounds thereof with acetylacetone, neodymium tri-n-butoxide, and the like. It is done. These components (a) may be used alone or in combination of two or more.
  • the component (b) used in the coordination polymerization is selected from organoaluminum compounds.
  • organoaluminum compound a trihydrocarbyl aluminum compound represented by the formula: R 12 3 Al, a hydrocarbyl aluminum hydride represented by the formula: R 12 2 AlH or R 12 AlH 2 (in the formula, R 12 are each independently a hydrocarbon group having 1 to 30 carbon atoms), hydrocarbylaluminoxane compounds having a hydrocarbon group having 1 to 30 carbon atoms, and the like.
  • the organoaluminum compound include trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, and alkylaluminoxane. These compounds may be used alone or in combination of two or more.
  • (b) component it is preferable to use aluminoxane and another organoaluminum compound in combination.
  • the component (c) used in the coordination polymerization is a compound having a hydrolyzable halogen or a complex compound thereof with a Lewis base; an organic halide having a tertiary alkyl halide, benzyl halide or allyl halide; a non-coordinating anion And an ionic compound comprising a counter cation.
  • Specific examples of the component (c) include alkylaluminum dichloride, dialkylaluminum chloride, silicon tetrachloride, tin tetrachloride, zinc chloride and Lewis base complexes such as alcohol, magnesium chloride and alcohol such as Lewis.
  • Examples thereof include complexes with bases, benzyl chloride, t-butyl chloride, benzyl bromide, t-butyl bromide, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. These components (c) may be used alone or in combination of two or more.
  • the polymerization initiator is preliminarily used by using the same conjugated diene compound and / or non-conjugated diene compound as the polymerization monomer, if necessary, in addition to the components (a), (b) and (c). May be prepared. Further, part or all of the component (a) or the component (c) may be supported on an inert solid. The amount of each of the above components can be set as appropriate. Usually, the component (A) is 0.001 to 0.5 mmol (mmol) per 100 g of the monomer. Further, in terms of molar ratio, (b) component / (b) component is preferably 5 to 1,000, and (c) component / (b) component is preferably 0.5 to 10.
  • the polymerization temperature in the coordination polymerization is preferably in the range of ⁇ 80 to 150 ° C., more preferably in the range of ⁇ 20 to 120 ° C.
  • a hydrocarbon solvent inert to the reaction exemplified in the above-mentioned anionic polymerization can be used, and the concentration of the monomer in the reaction solution is the same as in the case of anionic polymerization.
  • the reaction pressure in coordination polymerization is the same as that in the case of anionic polymerization, and it is desirable that the raw material used for the reaction substantially removes reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds.
  • the modified conjugated diene polymer is preferably an anion-polymerized organic alkali metal compound, particularly alkyllithium.
  • the content of the aromatic vinyl compound unit is 0% by mass or more and 60% by mass as an unmodified and / or modified low molecular weight diene copolymer in the form of an unmodified product or before modification. %, More preferably 1% by mass to 60% by mass, and the vinyl bond content of the conjugated diene moiety is preferably 5% by mass to 80% by mass. If the content of the aromatic vinyl compound unit and the vinyl bond content of the conjugated diene compound portion are not within the above ranges, sufficient compatibility between ensuring the workability of the rubber composition and reducing the loss tangent (tan ⁇ ) of the rubber composition is achieved. It may not be possible.
  • the content of the aromatic vinyl compound unit is more preferably 10% by mass to 50% by mass, and the vinyl bond content of the conjugated diene moiety is preferably 10% by mass to 70% by mass.
  • the conjugated diene polymer in the present invention is a modified conjugate obtained by subjecting a polymerization active terminal to a compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom after the polymerization reaction.
  • a diene polymer is preferred.
  • the conjugated diene polymer having a polymerizable active terminal is conjugated with an aromatic vinyl compound using an organic alkali metal compound, preferably a lithium compound, as described in the production of the conjugated diene polymer.
  • the diene compound can be obtained by anionic polymerization in the same manner as described above.
  • the reaction conditions are appropriately selected so that the resulting low molecular weight diene copolymer having an active terminal has the above-described properties.
  • Nitrogen-containing compounds, silicon-containing compounds, tin-containing compounds, and the like can be used as modifiers that are reacted with the active ends of the low molecular weight diene copolymer thus obtained.
  • nitrogen-containing compounds examples include bis (diethylamino) benzophenone, dimethylimidazolidinone, N-methylpyrrolidone, 4-dimethylaminobenzylideneaniline, and the like.
  • functional groups containing nitrogen such as substituted and unsubstituted amino groups, amide groups, imino groups, imidazole residues, nitrile groups, and pyridyl groups can be introduced.
  • the low molecular weight diene copolymer having an active terminal to be used is preferably such that at least 10% of the polymer chain has a living property.
  • the first modified conjugated diene polymer to be a conjugated diene copolymer is the following with respect to the conjugated diene polymer having an organometallic active site in the molecule thus obtained.
  • a + b + c 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and D is a saturated cyclic tertiary amine compound]
  • Residue unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group , Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid ester residue, metal salt of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, carboxylic acid halogen It is a compound residue and at least one functional group selected from a secondary amino group or a mercapto group having a hydroly
  • R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R 1 is plural. May be different.
  • R 2 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 2 is plural, they are the same or different.
  • R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 3 is plural, they may be the same or different. Good. It can be obtained by reacting a modifier represented by
  • R 1 and R 2 are each an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aryl group having 7 to 18 carbon atoms.
  • Aralkyl group and the like can be mentioned.
  • the alkyl group and alkenyl group may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group.
  • the aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the divalent inert hydrocarbon group having 1 to 20 carbon atoms in R 3 is preferably an alkylene group having 1 to 20 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, but a linear one is particularly preferable.
  • Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.
  • Examples of the saturated cyclic tertiary amine compound residue in D include a hexamethyleneimino group, a pyrrolidinyl group, a piperidinyl group, a heptamethyleneimino group, and a dodecamethyleneimino group.
  • Examples of amine compound residues include imidazole residues, dihydroimidazole residues, oxazole residues, and pyridyl groups.
  • the D includes a ketimine residue, a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, a pyridine group, a nitrile group, an isocyanate group, and a detachable functional group from the viewpoint of performance. It is preferably a monovalent group having at least one nitrogen-containing functional group selected from secondary amino groups, saturated cyclic tertiary amine compound residue, ketimine residue, imidazole residue, dihydroimidazole residue and It is more preferably a monovalent group having at least one selected from secondary amino groups having a detachable functional group.
  • the imine residue includes ketimine, aldimine and amidine residues
  • the (thio) carboxylic acid hydrocarbyl ester is unsaturated such as acrylate or methacrylate.
  • residues of carboxylic acid esters examples include alkali metals, alkaline earth metals, aluminum, tin, and zinc.
  • examples of the secondary amino group having a hydrolyzable group include N- (trimethylsilyl) amino group.
  • the (thio) isocyanate group is a —NCO group or a —NCS group.
  • examples of the monovalent group containing a (thio) epoxy group include glycidoxy group, 3,4-epoxycyclohexyl group, and those obtained by replacing the epoxy ring in these groups with a thioepoxy ring.
  • the modifier used in the conjugated diene polymer is a bifunctional hydrocarbyloxysilane compound and / or a partial condensate thereof as described above.
  • the partial condensate means a product in which a part (not all) of the SiOR groups of the hydrocarbyloxysilane compound are bonded by SiOSi by condensation.
  • the modifier used is a monofunctional hydrocarbyloxysilane compound having one hydrocarbyloxy group directly bonded to a silicon atom, the hydrocarbyloxy group is consumed by the modification reaction and interacts with an inorganic filler such as silica. Since the modifying group to be introduced is not introduced, the object of the present invention cannot be achieved.
  • a conjugated diene polymer having a plurality of active ends reacts with one molecule of the modifier, whereby Highly efficient introduction of modified ends per molecule cannot be achieved.
  • the conjugated diene polymer having an active terminal to be used is preferably one in which at least 10% of the polymer chains have living properties.
  • hydrocarbyloxysilane compound represented by the general formula (VI) examples include, for example, (thio) epoxy group-containing hydrocarbyloxysilane compounds such as 2-glycidoxyethyltrimethoxysilane and 2-glycidoxyethyltriethoxysilane.
  • Examples of the imine (amidine) residue-containing compound include 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -4,5- Dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxysilylpropyl) Examples include -4,5-dihydroimidazole, and among these, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is preferable.
  • bifunctional hydrocarbyloxysilane compound represented by the general formula (VI) for example, when D has an imidazole residue or a dihydroimidazole residue, as a specific example, 1- [3- [diethoxy (methyl) silyl] Propyl] -imidazole, 1- [3- [diethoxy (ethyl) silyl] propyl] -imidazole, 1- [3- [dipropoxy (methyl) silyl] propyl] -imidazole, 1- [3- [dipropoxy (ethyl) silyl ] Propyl] -imidazole, 1- [3- [diethoxy (methyl) silyl] propyl] -4,5-dihydroimidazole, 1- [3- [diethoxy (ethyl) silyl] propyl] -4,5-dihydroimidazole, 1- [3- [diethoxy (ethyl) silyl] propyl] -4,5
  • bifunctional hydrocarbyloxysilane compound represented by the general formula (VI) for example, when D has a pyridyl group or a nitrile group, as a specific example, 2- [2- [diethoxy (methyl) silyl] ethyl] -Pyridine, 2- [2- [dipropoxy (methyl) silyl] ethyl] -pyridine, 2- [3- [diethoxy (methyl) silyl] propyl] -pyridine, 2- [3- [diethoxy (ethyl) silyl] propyl ] -Pyridine, 2- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 2- [3- [dipropoxy (ethyl) silyl] propyl] -pyridine, 4- [2- [diethoxy (methyl) silyl] Ethyl] -pyridine, 4- [2- [diethoxy (methyl) silyl] Ethyl] -
  • 2- [3- [diethoxy (methyl) silyl] propyl] -pyridine 2- [3- [dipropoxy (methyl) silyl] propyl] -pyridine
  • 4- [3- [diethoxy (methyl) silyl] ] Propyl] -pyridine 4- [3- [dipropoxy (methyl) silyl] propyl] -pyridine
  • 1-cyano-3- [diethoxy (methyl) silyl] -propane and 1-cyano-3- [dipropoxy (methyl) Silyl] -propane is preferred.
  • bifunctional hydrocarbyloxysilane compound represented by the general formula (VI) for example, when D has a (thio) isocyanate group or an oxazole residue, as a specific example, 1-isocyanato-3- [diethoxy (methyl ) Silyl] -propane, 1-isocyanato-3- [diethoxy (ethyl) silyl] -propane, 1-isocyanato-3- [dipropoxy (methyl) silyl] -propane, 1-isocyanato-3- [dipropoxy (ethyl) silyl ]
  • Isocyanate compounds such as propane, thioisocyanate compounds in which the isocyanate in the above isocyanate compounds is replaced by thioisocyanate, 4- [3- [diethoxy (methyl) silyl] propyl] -oxazole, 4- [3- [diethoxy ( Ethyl) silyl] propyl] -oki Te
  • the oxazole residue also includes an isoxazole residue.
  • hydrocarbyloxysilane compounds include the following. That is, as the carboxylic acid hydrocarbyl ester residue-containing compound, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyl Examples thereof include triisopropoxysilane, among which 3-methacryloyloxypropyltrimethoxysilane is preferable.
  • Examples of the isocyanate group-containing compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and 3-isocyanatopropyltriisopropoxysilane. Of these, 3-isocyanatopropyltriethoxysilane is preferred.
  • the hydrocarbyloxysilane compound having the above characteristic structure is preferably added in a stoichiometric amount or in excess of the active site, more preferably 0.3 molar equivalent or more of the apparent active site. (Normally, one mole of the modifying hydrocarbyloxysilane compound corresponds to several mole equivalents of the active site), the hydrocarbyloxysilane compound is reacted with the active site, and the active site is substantially hydrocarbyloxysilane compound. After introducing the residue, a method of adding a condensation accelerator is used.
  • condensation accelerator examples include a compound containing a tertiary amino group, or among group 3, 4, 5, 12, 13, 14, and 15 of the periodic table (long period type).
  • An organic compound containing one or more elements belonging to any of the above can be used.
  • the condensation accelerator used here can be added before the modification reaction, but is preferably added to the modification reaction system during and / or after the modification reaction.
  • the condensation accelerator When added before the denaturation reaction, a direct reaction with the active end occurs, and for example, a hydrocarboxy group having a protected primary amino group at the active end may not be introduced. It is preferable to add the condensation accelerator to the reaction system immediately after the modification in which the hydrocarbylsilane compound residue is introduced. However, the polymer modified by the reaction is dried and then blended, preferably blended. In the first stage, a condensation accelerator may be added. In this modification reaction, the conjugated diene polymer used preferably has at least 20% of polymer chains having the active site.
  • the second modified conjugated diene polymer in the present invention has the following general formula (IV) at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
  • R a MX b ......... (IV) [In the formula (IV), each R independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl having 7 to 20 carbon atoms. Selected from the group, M is tin or silicon, and X is independently chlorine, bromine or iodine.
  • A is an integer of 0 to 3
  • R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 carbon atoms. Selected from ⁇ 20 aralkyl groups and M is tin or silicon.
  • A is an integer of 0 to 3
  • the method for producing the polymer having an organometallic active site in the molecule is the same as in the case of the first modified conjugated diene polymer.
  • the modified conjugated diene polymer modified with at least one of the coupling agents represented by the general formulas (IV) and (V) has at least one tin-carbon bond or silicon-carbon bond.
  • R or R 1 and R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms.
  • Group or an aralkyl group having 7 to 20 carbon atoms and specific examples thereof include a methyl group, an ethyl group, an n-butyl group, a neophyll group, a cyclohexyl group, an n-octyl group, and a 2-ethylhexyl group.
  • M is tin or silicon, and X is independently chlorine, bromine or iodine.
  • a is an integer of 0 to 3
  • tin tetrachloride As the coupling agent represented by the general formula (IV), tin tetrachloride, RSnCl 3 , R 2 SnCl 2 , R 3 SnCl and the like are preferable, and tin tetrachloride is particularly preferable.
  • tetraalkoxysilane, trialkoxysilane, and dialkoxysilane are preferable, and tetraethoxysilane is particularly preferable.
  • the third modified diene polymer in the present invention is a modification obtained by reacting a condensate of an alkoxysilane compound represented by the general formula (VI) with a modifier represented by the general formula (VI). It is a conjugated diene polymer.
  • the alkoxysilane compound represented by the general formula (V) and the modifier represented by the general formula (VI) are as described above.
  • the method for producing the polymer having an organometallic active site in the molecule is the same as in the case of the first modified conjugated diene polymer. Further, the kind of the condensation accelerator and the condensation reaction conditions are also as described in the production of the first modified conjugated diene polymer.
  • the modified conjugated diene polymer in the present invention modified with the modifier described above contains a nitrogen atom.
  • a white filler such as silica is blended with a rubber component containing a modified conjugated diene polymer having a nitrogen-containing functional group
  • the dispersibility of the white filler such as silica in the rubber component is improved.
  • the hysteresis loss of the rubber component is reduced, the low loss performance can be remarkably improved. Therefore, in the present invention, by using a modified conjugated diene polymer having a nitrogen-containing functional group together with a white filler such as silica, the dispersibility of the white filler such as silica is greatly improved.
  • the low loss performance in the rubber composition can be remarkably improved while sufficiently exerting the reinforcing effect of the white filler.
  • the modification reaction for obtaining the first modified conjugated diene polymer and the second modified conjugated diene polymer can be carried out using either a solution reaction or a solid phase reaction. It may contain unreacted monomers used during the polymerization.).
  • a solution reaction or a solid phase reaction It may contain unreacted monomers used during the polymerization.
  • denaturation reaction You may carry out using a batch type reactor, You may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor and an in-line mixer.
  • the temperature of the modification reaction is preferably 20 ° C. or higher, but the polymerization temperature of the conjugated diene polymer can be used as it is, and a more preferable range is 30 to 120 ° C.
  • the amount of the modifier used is preferably in the range of 0.25 to 3.0 mol, more preferably in the range of 0.5 to 1.5 mol, relative to 1 mol of the polymerization initiator used for the production of the conjugated diene polymer. .
  • the modification with the modifier is performed on the active site in the conjugated diene polymer, but the active site may be in the polymer molecule, and the position thereof is not particularly limited.
  • the rubber component contains a modified conjugated diene polymer obtained by modifying at least one molecular terminal with a modifier composed of a compound containing a functional group that interacts with a white filler such as silica. From the viewpoint of low loss performance of the obtained rubber composition for tires, it is particularly preferable, and from this viewpoint, the active site in the polymer is preferably present at the end of the conjugated diene polymer.
  • the rubber composition for tires of the present invention contains the above-mentioned modified conjugated diene polymer (first polymer, second polymer) as a rubber component.
  • the content of the modified conjugated diene polymer in the rubber component (A) is preferably in the range of 5 to 80 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the content of the modified conjugated diene polymer in the rubber component is 5 parts by mass or more, the effect of improving the dispersibility of the white filler such as silica can be exhibited, while 80 parts by mass or less. By doing so, the effect of the present invention can be exhibited without deteriorating workability.
  • the content is more preferably in the range of 15 parts by mass or more and 60 parts by mass or less.
  • examples of the white filler used in the tire rubber composition of the present invention include silica, aluminum hydroxide, alumina, clay, calcium carbonate and the like. Among these, silica and hydroxide are used from the viewpoint of reinforcement. Aluminum is preferred and silica is particularly preferred. Silica that can be used is not particularly limited, and those used in commercially available rubber compositions can be used, among which wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), colloidal silica, etc. are used. In particular, the use of wet silica is preferred.
  • the content of these white fillers is preferably in the range of 5 to 200 parts by weight, more preferably in the range of 10 to 150 parts by weight, even more preferably, with respect to 100 parts by weight of the rubber component. , Preferably in the range of 20 to 120 parts by mass. In particular, in the case of the present invention, the effect of the present invention can be exhibited even if the silica content is as high as 60 parts by mass or more based on 100 parts by mass of the rubber component.
  • the content of the white filler is preferably 5 parts by mass or more from the viewpoint of improving the fracture characteristics with respect to 100 parts by mass of the rubber component, and is preferably 200 parts by mass or less from the viewpoint of workability.
  • silica is used as the white filler to be used, it is preferable to use a silane coupling agent from the viewpoint of reinforcing properties.
  • the silane coupling agent that can be used is not particularly limited, and examples thereof include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, and bis (3-triethoxysilylpropyl) disulfide.
  • the content of these silane coupling agents varies depending on the content of silica, but is preferably 1 to 20 parts by weight, more preferably 6 parts from the viewpoint of heat generation, with respect to 100 parts by weight of silica. A range of ⁇ 12 parts by weight is desirable.
  • the content of the silane coupling agent is preferably 1 part by mass or more from the viewpoint of the effect of adding the coupling agent to 100 parts by mass of silica, and from the viewpoint of maintaining reinforcement and exothermicity, the content is 20 parts by mass or less. preferable.
  • carbon black or the like can be used as a reinforcing filler in addition to the white filler.
  • Carbon black that can be used is not particularly limited, and grades such as FEF, SRF, HAF, ISAF, and SAF can be used.
  • the content of these carbon blacks is also not particularly limited, but is preferably 0 to 250 parts by weight, more preferably 10 to 250 parts by weight with respect to 100 parts by weight of the rubber component. .
  • 200 parts by mass or less is preferable.
  • R 1 represents an alkyl or alkenyl group having 1 to 24 carbon atoms, a group represented by the following formula (III), wherein the alkyl group and alkenyl group are linear or branched.
  • R 2 and R 3 may be a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit, and these may be the same or different.
  • R 4 represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic, and , R 5 is a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit.
  • A is a single bond or an alkyl or alkenyl group having 1 to 24 carbon atoms
  • B is a carbonyl group, an ester group, an amino group, an amide group, an ether group, a hydroxyl group
  • R 6 represents a C 1-24 alkyl group or alkenyl group
  • the alkyl group and alkenyl group may be linear, branched, or cyclic.
  • R 1 represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, or a group represented by the above formula (III).
  • the alkyl group and alkenyl group having 1 to 24 carbon atoms may be linear, branched, or cyclic.
  • alkenyl groups such
  • Preferred examples of the fatty acid used as a raw material include octanoic acid, lauric acid, tetradecanoic acid, myristic acid, stearic acid, and oleic acid.
  • R 1 is a group represented by the above formula (III)
  • A is a single bond or an alkyl or alkenyl group having 1 to 24 carbon atoms
  • B is a carbonyl group.
  • R 6 is an alkyl group or alkenyl group having 1 to 24 carbon atoms as in R 1 above.
  • the alkyl group and alkenyl group may be linear, branched or cyclic.
  • preferable compounds include the following compounds (1) to (5).
  • R 1 is the above-mentioned alkyl group or alkenyl group having 1 to 24 carbon atoms (including linear, branched and cyclic)
  • R 2 is a hydroxyalkyl group
  • R 7 is an alkylene group having 1 to 6 carbon atoms]
  • R 3 is a hydroxyalkyl group, a hydroxy having an oxyalkylene unit.
  • Examples thereof include an amine compound having an alkyl group [— (R 8 O) n—H: R 8 is an alkylene group having 1 to 6 carbon atoms, and m + n is a number of 1 to 20].
  • Specific examples of amine compounds that can be used in this compound include N-tridecylethanolamine, N-octylethanolamine, N-laurylethanolamine, N-decylethanolamine, N-dodecylethanolamine, N-alkylethanolamines such as N-tetradecylethanolamine, N-hexadecylethanolamine, N-octadecylethanolamine, N-octadecenylethanolamine, N-alkenylethanolamine, POE (2) octylamine, POE (4) Decylamine, POE (2) dodecylamine, POE (5) dodecylamine, POE (15) dodecylamine, POE (2) tetradecylamine,
  • R 1 and R 2 represents a group represented by the following formula (VII), and at least one of R 2 and R 3 represents the following formula ( VIII).
  • R 9 represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, and the alkyl group and alkenyl group may be any of linear, branched, and cyclic
  • R 10 is an alkylene group having 1 to 6 carbon atoms
  • y means an average number of added moles and is a number from 0 to 5
  • z is from 1 to 3. Examples include amine derivatives that become integers.
  • amine derivatives contained in this compound include N-lauroylaminopropyl-N, N-dimethylamine, N-lauroylaminoethyl-N, N-diethylamine, N-lauroylaminopropyl-N, N-diethylamine, N-palmitoylaminopropyl-N, N-dimethylamine, N-palmitoylaminoethyl-N, N-diethylamine, N-stearoylaminopropyl-N, N-dimethylamine, N-stearoylaminoethyl-N, Examples thereof include at least one of N-diethylamine, di (N-lauroylaminoethyl) -N-methylamine, and tri (N-lauroylaminoethyl) amine.
  • N-lauroylaminopropyl-N, N-dimethyl Amine, N-lauroylaminoethyl- , N-diethylamine, N-palmitoylaminopropyl-N, N-dimethylamine, N-palmitoylaminoethyl-N, N-diethylamine, N-stearoylaminopropyl-N, N-dimethylamine, and N-stearoylaminoethyl- N, N-diethylamine and the like can be mentioned.
  • combining method of the said compound is known, can be obtained by various manufacturing methods, and may use a commercially available thing.
  • R 1 is a group represented by the formula (III).
  • A is a single bond
  • B is a carbonyl group (—CO—)
  • R 6 is an alkyl group or alkenyl group having 1 to 24 carbon atoms (including linear, branched and cyclic)
  • R 2 is a hydroxyalkyl group or a hydroxyalkyl group having an oxyalkylene unit [— ( R 7 O) n—H: R 7 is an alkylene group having 1 to 6 carbon atoms, n is a number of 1 to 5], and monoalkanolamide in which R 3 is a hydrogen atom.
  • monoalkanolamides that can be used in this compound include octanoic acid monoethanolamide, octanoic acid monoisopropanepropanolamide, POE (2) octanoic acid monoethanolamide, lauric acid monoethanolamide, lauric acid Mention may be made of at least one of monoisopropanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, POE (2) lauric acid monoethanolamide, among which lauric acid monoisopropanolamide, lauric acid monoethanolamide, stearic acid It is desirable to use monoethanolamide, oleic acid monoethanolamide, POE (2) lauric acid monoethanolamide.
  • the synthesis method of the said monoalkanolamide is known, can be obtained by various manufacturing methods, and may use a commercially available thing.
  • R 1 is a group represented by the formula (III).
  • A is a single bond
  • B is a carbonyl group (—CO—)
  • R 6 is an alkyl group or alkenyl group having 1 to 24 carbon atoms (including linear, branched and cyclic)
  • R 2 and R 3 are each independently a hydroxyalkyl group or an oxyalkylene unit.
  • dialkanolamides contained in this compound include octanoic acid diethanolamide, octanoic acid diisopropanolamide, lauric acid diethanolamide, POE (5) lauric acid diethanolamide, stearic acid diethanolamide, There may be mentioned at least one of oleic acid diethanolamide and POE (5) oleic acid diethanolamide. Among them, lauric acid diethanolamide, stearic acid diethanolamide, and oleic acid diethanolamide are preferable.
  • the synthesis method of the said dialkanolamide is known, can be obtained by various manufacturing methods, and may use a commercially available thing.
  • R 4 is an alkyl group or alkenyl group having 1 to 24 carbon atoms (including linear, branched and cyclic) as in R 1 above.
  • R 5 may be an imidazoline compound which is a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit.
  • imidazoline compounds contained in this compound include 1-hydroxyethyl-2-undecylimidazoline, 1-hydroxyethyl-2-methylimidazoline, 1-hydroxyethyl-2-propylimidazoline, Hydroxyethyl-2-heptyluimidazoline, 1-hydroxyethyl-2-nonylimidazoline, 1-hydroxyethyl-2-undecylimidazoline, 1-hydroxypropyl-2-methylimidazoline, 1-hydroxypropyl-2-propylimidazoline, 1 -Hydroxypropyl-2-heptylimidazoline, 1-hydroxypropyl-2-nonylimidazoline, 1-hydroxypropyl-2-undecylimidazoline, 1-hydroxybutyl-2-undecylimidazoline, etc. It is.
  • combining method of the said imidazoline compound is known, can be obtained by various manufacturing methods, and may use a commercially available thing
  • the (total) content of the compounds represented by the above formula (I), formula (II) and the like is preferably 0.5 to 15 parts by mass, more preferably 100 parts by mass with respect to the rubber component. From the viewpoint of exerting further effects of the present invention, 1 to 15 parts by mass is preferable, and 1 to 10 parts by mass is more preferable. Further, the content of these compounds is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 12 parts by mass with respect to 100 parts by mass of the white filler.
  • a compounding agent usually used in the rubber industry for example, an antioxidant, a softener, stearic acid, zinc white, a vulcanization accelerator, a vulcanization accelerator, a vulcanizer, and the like may be appropriately selected and contained within a range that does not impair the object of the present invention. it can.
  • a compounding agent usually used in the rubber industry, For example, an antioxidant, a softener, stearic acid, zinc white, a vulcanization accelerator, a vulcanization accelerator, a vulcanizer, and the like may be appropriately selected and contained within a range that does not impair the object of the present invention. it can.
  • these compounding agents commercially available products can be suitably used.
  • the rubber composition for tires of the present invention includes a rubber component, a white filler, a compound represented by the above formula (I), formula (II) and the like, and various compounding agents appropriately selected as necessary.
  • the rubber composition for tires thus configured improves the dispersibility of white dispersants such as silica in the rubber composition for tires and significantly improves the low loss performance is as follows. Is inferred. That is, in the rubber composition for a tire of the present invention, the rubber component containing the conjugated diene polymer having the above characteristics improves the dispersibility of a white filler such as silica. That is, when a white filler such as silica is added to the rubber component containing the conjugated diene polymer having the above characteristics, the surface area of the white filler increases, and the surface area of the white filler such as silica increases.
  • the reaction point of the silica dispersant (hydrophobizing agent) composed of the compound represented by the above formula (I), formula (II) or the like increases.
  • white fillers such as silica with a silica dispersant (hydrophobizing agent) comprising a compound represented by formula (I), formula (II), etc.
  • the dispersibility of the white filler is further improved.
  • the tire of this invention is manufactured by a normal method using the rubber composition for tires of this invention. That is, if necessary, the tire rubber composition of the present invention containing various compounding agents as described above is extruded into a tread member, for example, as a tire member at an unvulcanized stage, and a tire molding machine The above is pasted and molded by a usual method to form a green tire. The green tire is heated and pressed in a vulcanizer to obtain a tire. Since the tire of the present invention thus obtained is excellent in low heat build-up, the low loss performance is very good, and the processability of the rubber composition is good, so that the productivity is also excellent. It will be a thing.
  • gas with which the tire of the present invention is filled normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen is exemplified.
  • reaction temperature was lowered to 200 ° C. and the pressure was lowered to 200 mmHg over 1.5 hours, and aging was performed for 1 hour under these conditions. Further, the pressure was lowered to 10 mmHg over about 1.5 hours, and the reaction was carried out for 1 hour under these conditions to remove excess AEEA, thereby obtaining 253 g of 1-hydroxyethyl-2-undecylimidazoline.
  • Examples 1 to 27 and Comparative Examples 1 to 17 The rubber composition was prepared by mixing the components of the first stage type and amount with the compounding formulations shown in Tables 1 to 3 below, and then kneading the components of the second stage type and amount. It was done by doing. About each obtained rubber composition for tires, it evaluated by the following measuring method by the low fuel consumption property which is low loss performance. These results are shown in Tables 1 to 3 below.
  • * 1 to * 12 are as follows.
  • * 1 Solution polymerization SBR manufactured by Asahi Kasei Co., Ltd., trade name “Toughden 2000”
  • * 2 Product name “# 80” manufactured by Asahi Carbon Co., Ltd.
  • the rubber composition for tires of the present invention can be suitably used for tire members of pneumatic tires such as tire treads, under treads, carcass, sidewalls, and bead portions.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Pour fournir une composition de caoutchouc pour pneus, qui a une faible tangente de perte remarquablement améliorée par amélioration de la dispersibilité d'une charge blanche telle que la silice, et un pneu utilisant la composition de caoutchouc pour pneus, cette composition de caoutchouc pour pneus est configurée pour contenir une charge blanche et au moins l'un des composés représentés par les formules (I) et (II) dans au moins un composant de caoutchouc (A) qui est choisi parmi les caoutchoucs naturels et/ou les caoutchoucs synthétiques à base de diène, le composant de caoutchouc (A) contenant un polymère diène conjugué qui a au moins un atome choisi parmi un atome de Si, un atome de Se, un atome de soufre, un atome d'oxygène et un atome de Ti à une extrémité terminale à activité de polymérisation ou une extrémité terminale initialisant la polymérisation ou dans une chaîne de polymère. (Dans la formule (I), R1 représente un groupe alkyle ou alcényle linéaire, ramifié ou cyclique, ayant 1-24 atomes de carbone ou un groupe représenté par la formule (III) ; et chacun de R2 et R3 représente un atome d'hydrogène, un groupe hydroxyle, un groupe hydroxyalkyle ou un groupe hydroxyalkyle ayant une unité oxyalkylène, et R2 et R3 peuvent être identiques ou différents l'un de l'autre.) (Dans la formule (II), R4 est le même que le R1 décrit ci-dessus ; R5 représente un groupe hydroxyle, un groupe hydroxyalkyle ou un groupe hydroxyalkyle ayant une unité oxyalkylène.) (Dans la formule (III), A représente une simple liaison ou un groupe alkyle ou alcényle ayant 1-24 atomes de carbone ; B représente un groupe carbonyle, un groupe ester, un groupe amino, un groupe amide, un groupe éther, un groupe hydroxyle, un groupe hydroxyalkyle ou un groupe hydroxyalkylène ; et R6 est le même que le R1 décrit ci-dessus).
PCT/JP2012/083103 2011-12-20 2012-12-20 Composition de caoutchouc pour pneus et pneu l'utilisant WO2013094693A1 (fr)

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